CN117957920A - Apparatus, system and method for producing hydrogen peroxide, hydrocarbons and synthesis gas - Google Patents
Apparatus, system and method for producing hydrogen peroxide, hydrocarbons and synthesis gas Download PDFInfo
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- CN117957920A CN117957920A CN202280061853.9A CN202280061853A CN117957920A CN 117957920 A CN117957920 A CN 117957920A CN 202280061853 A CN202280061853 A CN 202280061853A CN 117957920 A CN117957920 A CN 117957920A
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- 239000007789 gas Substances 0.000 title claims abstract description 179
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 40
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 title claims description 31
- 238000003786 synthesis reaction Methods 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title description 18
- 239000007788 liquid Substances 0.000 claims abstract description 78
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 172
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 138
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 78
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 29
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 28
- 239000012530 fluid Substances 0.000 claims description 25
- 235000006408 oxalic acid Nutrition 0.000 claims description 25
- 238000004891 communication Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 14
- 235000019253 formic acid Nutrition 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011149 active material Substances 0.000 claims description 7
- 239000012736 aqueous medium Substances 0.000 claims description 7
- 239000011324 bead Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 210000002381 plasma Anatomy 0.000 description 50
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 13
- 239000002609 medium Substances 0.000 description 12
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000000446 fuel Substances 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- -1 CH 4 Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011002 quantification Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 238000003149 assay kit Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000037361 pathway Effects 0.000 description 3
- 238000000678 plasma activation Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910003080 TiO4 Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000004139 low temperature NMR Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 238000002407 reforming Methods 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/247—Generating plasma using discharges in liquid media
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
- C01B15/0275—Preparation by reaction of water, carbon monoxide and oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
- C01B3/045—Decomposition of water in gaseous phase
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/06—Oxalic acid
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/2406—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
- B01J2219/00279—Features relating to reactor vessels
- B01J2219/00306—Reactor vessels in a multiple arrangement
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00853—Employing electrode arrangements
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
- B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
- B01J2219/0809—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes employing two or more electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0869—Feeding or evacuating the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J2219/0873—Materials to be treated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J2219/0873—Materials to be treated
- B01J2219/0892—Materials to be treated involving catalytically active material
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/2402—Monolithic-type reactors
- B01J2219/2425—Construction materials
- B01J2219/2427—Catalysts
- B01J2219/243—Catalyst in granular form in the channels
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0861—Methods of heating the process for making hydrogen or synthesis gas by plasma
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/86—Carbon dioxide sequestration
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H2245/00—Applications of plasma devices
- H05H2245/10—Treatment of gases
- H05H2245/17—Exhaust gases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Plasma-bubble reactors, reactor systems, and methods for producing hydrogen peroxide (H 2O2), one or more hydrocarbons, and syngas are disclosed. The reactor comprises a vessel configured to hold a liquid; and a plasma generating device associated with the vessel, the plasma generating device configured to receive an input feed comprising carbon dioxide (CO 2) gas and generate a plasma from the CO 2 gas to produce an activated CO 2 gas encapsulated within a plurality of bubbles formed in the liquid, wherein the activated CO 2 gas is reacted with water (H 2 O) at a plasma-liquid interface formed between the bubbles and surrounding liquid to produce hydrogen peroxide (H 2O2), one or more hydrocarbons, and syngas.
Description
Technical Field
The present invention relates to an apparatus, system and method for producing hydrogen peroxide, one or more hydrocarbons and synthesis gas.
The present invention has been developed primarily for use in the production of precursors useful in the chemical industry and will be described hereinafter with reference to this application. However, it should be understood that the present invention is not limited to this particular field of use.
Background
The average concentration of carbon dioxide (CO 2) in the global biosphere has increased from 280ppm in the middle of the 18 th century to 416ppm in 2021, mainly due to human activity, especially the combustion of fossil fuels (e.g., coal, oil and natural gas). The increasing concentration of CO 2 has raised a number of problems including global warming, desertification and marine acidification. In response to these problems, in recent years, particularly under the push of achieving global emission reduction objectives and paris agreement commitments in various countries, development of innovative technologies for greatly reducing CO 2 emissions has been receiving attention and has made substantial progress.
The main challenge in converting CO 2 is to overcome the high stability of the CO 2 molecule-in other words, break the linear and central symmetrical double bonds (o=c=o). Conventional strategies for converting CO 2 to value-added chemicals or renewable fuels (e.g., CO, CH 4, and liquid chemicals) have been studied and developed, including primarily thermocatalytic, electrocatalytic, and photocatalytic processes. However, the production of fuels and chemicals based on these methods is energy intensive and, more importantly, some processes consume large amounts of valuable high purity hydrogen.
In recent years, non-thermal plasmas (NTPs) generated by applying electrical energy to a feed gas have proven to be an effective tool in providing an attractive solution for activating inert CO 2 molecules into a more reactive, vibrational or electronically excited state to promote CO 2 molecular dissociation, thereby promoting highly stable double bond (o=c=o) cleavage.
The use of NTP has resulted in the efficient conversion of CO 2 to higher value chemicals and fuels. The energetic electrons generated in NTP have an average electron temperature of 1-10eV and are able to activate CO 2 molecules by ionization, excitation, and dissociation, producing a large number of active species (e.g., excited atoms, ions, molecules, and radicals), which can initiate and propagate chemical reactions. The main challenges for converting CO 2 using NTP are to increase energy efficiency, to increase the competitiveness of the plasma process, and to selectively generate chemical compounds.
The present invention aims to provide an apparatus, system and method for producing hydrogen peroxide, one or more hydrocarbons and synthesis gas that will overcome or substantially ameliorate at least some of the disadvantages of the prior art, or at least provide an alternative.
It will be appreciated that if any prior art information is referred to herein, such reference does not constitute an admission that the information forms a part of the common general knowledge in the art in australia or any other country.
Disclosure of Invention
According to a first aspect of the present invention there is provided a plasma-bubble reactor comprising:
-a container configured for containing a liquid; and
A plasma generating device associated with the vessel configured to receive an input feed comprising carbon dioxide (CO 2) gas and generate a plasma from the CO 2 gas to produce an activated CO 2 gas encapsulated within a plurality of bubbles formed in a liquid,
-Wherein the activated CO 2 gas is reacted with water (H 2 O) at the plasma-liquid interface formed between the bubbles and the surrounding liquid to produce hydrogen peroxide (H 2O2), one or more hydrocarbons and synthesis gas.
In one embodiment, the plasma-generating device comprises two electrodes, wherein at least one of the two electrodes is a High Voltage (HV) electrode at least partially submerged within the liquid and configured for generating a discharge throughout the liquid when a potential difference is applied across the electrodes to activate CO 2 gas encapsulated within the gas bubble.
In one embodiment, each of the two electrodes is at least partially submerged within the liquid.
In one embodiment, each of the two electrodes is an HV electrode at least partially submerged in the liquid.
In one embodiment, the other of the two electrodes is a ground electrode electrically connected to the outer wall of the container.
Preferably, the HV electrode is partially enclosed within a tube defining a gas channel extending partially along the length of the HV electrode, wherein the tube is in fluid communication with the input feed and is provided with one or more outlets at a lower portion thereof to allow the activated CO 2 gas enclosed within the bubbles to be expelled therefrom into the liquid in the vessel.
Suitably, both electrodes are electrically connected to a DC or AC power supply.
In one embodiment, the reactor further comprises means for adjusting the vertical position of the HV electrode relative to the tube to produce a longer plasma flow within the gas channel.
Preferably, the vertical position of the HV electrode relative to the tube is adjustable in the range of about 0mm to about 60 mm.
In one embodiment, the tube of the HV electrode comprises a catalytically active material for catalyzing the reaction between the activated CO 2 gas and H 2 O.
In one form, the catalytically active material comprises a plurality of alumina beads.
In some embodiments, the one or more hydrocarbons are selected from the group consisting of formic acid, acetic acid, and oxalic acid.
In a preferred embodiment, the hydrocarbon is oxalic acid.
According to a second aspect of the present invention there is provided a reactor system comprising:
two or more plasma-bubble reactors, wherein each plasma-bubble reactor comprises:
-containers configured for containing liquids, wherein each container contains a plurality of ports;
-a plasma generating device associated with the vessel configured to receive an input feed comprising carbon dioxide (CO 2) gas and generate a plasma from the CO 2 gas to produce an activated CO 2 gas encapsulated within a plurality of bubbles formed in a liquid, wherein the activated CO 2 gas is reacted with water (H 2 O) at a plasma-liquid interface formed between the bubbles and surrounding liquid to produce hydrogen peroxide (H 2O2), one or more hydrocarbons and synthesis gas; and
-A plurality of fluid conduits, wherein each fluid conduit is configured for operatively coupling adjacent plasma-bubble reactors via a respective port such that one or more of CO 2 gas, H 2O2, one or more hydrocarbons, synthesis gas, and/or H 2 O are in fluid communication therebetween.
In one embodiment, the plasma generating device comprises two electrodes, wherein at least one of the two electrodes is a High Voltage (HV) electrode at least partially submerged within the liquid and configured for generating a discharge across the liquid when a potential difference is applied across the electrodes to activate CO 2 gas encapsulated within the gas bubble.
In one embodiment, the other of the two electrodes is a ground electrode electrically connected to the outer wall of the container.
Preferably, the reactor system further comprises a pump for fluidly communicating water from a water source to the vessel of one of the two or more plasma-bubble reactors.
Preferably, the reactor system further comprises a compressor for enhancing the flow of CO 2 gas from the input feed to the vessel of one of the two or more plasma-bubble reactors.
Preferably, the reactor system further comprises a flow rate meter arranged in line between the compressor and the vessel of one of the plasma-bubble reactors to monitor the flow rate of the CO 2 gas.
Preferably, the reactor system further comprises a liquid receiver for receiving H 2O2 from a vessel of one of the two or more plasma-bubble reactors.
In some embodiments, the one or more hydrocarbons are selected from the group consisting of formic acid, acetic acid, and oxalic acid.
In a preferred embodiment, the hydrocarbon is oxalic acid.
According to a third aspect of the present invention there is provided a process for producing hydrogen peroxide (H 2O2), one or more hydrocarbons and synthesis gas, the process comprising the steps of:
-generating a plasma from an input feed comprising carbon dioxide (CO 2) gas to produce an activated CO 2 gas encapsulated within a plurality of bubbles formed in a liquid; and
-Reacting the activated CO 2 gas with water (H 2 O) at a plasma-liquid interface formed between the bubbles and the surrounding liquid to produce hydrogen peroxide (H 2O2), one or more hydrocarbons and synthesis gas.
In one embodiment, the plasma is generated by applying a potential difference across two electrodes, wherein at least one of the two electrodes is a High Voltage (HV) electrode at least partially submerged within the liquid and configured for generating a discharge throughout the liquid to activate CO 2 gas encapsulated within the gas bubble.
In one embodiment, the discharge is a pulsed discharge.
Preferably, the potential difference is from about 5kV to about 100kV.
Preferably, the liquid is an aqueous medium.
Preferably, the aqueous medium comprises an electrolyte.
Preferably, the reaction is carried out in a vessel at substantially atmospheric pressure and room temperature.
In one embodiment, the input feed comprises a mixture of CO 2 gas and a second gas.
Preferably, the second gas is selected from the group consisting of carbon monoxide (CO), water vapor/water vapor (H 2 O), methane (CH 4), hydrogen (H 2), nitrogen (N 2), and any mixtures thereof.
In one embodiment, the HV electrode is partially enclosed within a tube defining a gas channel extending partially along the length of the HV electrode, the method further comprising the steps of:
adjusting the vertical position of the HV electrode relative to the vertical position of the tube to produce a longer plasma flow within the gas channel.
Preferably, the vertical position of the HV electrode is adjustable in a range of about 0mm to about 60mm relative to the vertical position of the tube.
In one embodiment, the method further comprises the steps of:
-catalysing the reaction between the activated CO 2 gas and H 2 O.
In some embodiments, the one or more hydrocarbons are selected from the group consisting of formic acid, acetic acid, and oxalic acid.
In a preferred embodiment, the hydrocarbon is oxalic acid.
Other aspects of the invention are also disclosed.
Drawings
While there are any other forms that can fall within the scope of the invention, a preferred embodiment of the invention will now be described, by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 shows a schematic diagram of a plasma-bubble reactor configured for activating carbon dioxide (CO 2) using a plasma to subsequently react with water (H 2 O) to produce hydrogen peroxide (H 2O2), oxalic acid (C 2H2O4), and syngas (CO, H 2, and O 2), in accordance with a preferred embodiment of the present invention;
FIG. 2 shows schematic diagrams of four (4) different configurations of the plasma-bubble reactor of FIG. 1, including (a) a reactor, (b) a reactor with adjustable High Voltage (HV) electrode height (h), (c) a reactor equipped with HV electrodes modified with catalyst, and (d) a reactor equipped with two (2) HV electrodes;
FIG. 3 shows a graph showing the gas ratios in the gas phase output from the reactions involving the plasma-bubble reactors of FIGS. 2 (a), 2 (b) and 2 (c) when the plasma driven process employs a CO 2 gas input feed;
Fig. 4 shows: (a) a renewable energy driven plasma microbubble reactor for generating underwater microbubbles for electroreduction of CO 2 to green fuel, (B) a graph of H 2O2 concentration in solution after plasma discharge (mg L -1) versus time (min), (C) a graph showing oxalic acid production rate (mg H -1) versus reduction flow rate (sccm) of CO 2, and (D) a graph showing H 2O2 production rate (mg H -1) versus reduction flow rate (sccm) of CO 2;
FIG. 5 shows electrical characteristics (5.8kV,1500Hz,35.5W,10sccm CO 2) of the plasma microbubble reactor of FIG. 4A;
FIG. 6 shows the effect of the pH of the CO 2 plasma discharge at different initial pH values on the following production rates (mg h -1): (a) formic acid and acetic acid concentrations (quantified by NMR, wherein (B) shows the NMR spectrum of the control group), (C) oxalic acid concentration (quantified by oxalate determination), and (D) H 2O2 concentration (measured by titanium (IV) sulfate method);
FIG. 7 shows a UV-Vis standard curve of H 2O2 concentration (mg L -1) at 410nm by titanium (IV) sulfate method;
FIG. 8 shows a graph of oxalic acid concentration (ppm) versus time (min) showing the dependence of oxalic acid production using the plasma microbubble reactor of FIG. 4A operating with the same profile of electrical characteristics (5.8kV,1500Hz,35.5W,10sccm CO 2) as in FIG. 5;
fig. 9 shows: (A) A graph showing the gas ratio (%) in the gas phase from the reaction output of the plasma-bubble reactor involved in fig. 4A when the plasma-driven process employs CO 2 gas input feed, and (B) a graph showing the decrease in CO 2 conversion (%) (diamond) with increasing CO 2 flow rate (sccm) and increasing CO energy efficiency (g kWh -1) (circle); and
Fig. 10 shows a schematic diagram of a plasma-bubble reactor system comprising three plasma-bubble reactors operably coupled via a plurality of fluid conduits such that one or more of CO 2 gas, H 2O2, one or more hydrocarbons, syngas, and/or H 2 O are in fluid communication therebetween, according to another preferred embodiment of the invention.
Detailed Description
It should be noted that in the following description, like or identical reference numerals designate identical or similar features in different embodiments.
The present invention is based on the discovery of a process for converting carbon dioxide (CO 2) gas into hydrogen peroxide (H 2O2) and synthesis gas, and one or more hydrocarbons including, but not limited to, formic acid (CH 2O2), acetic acid (CH 3 COOH) and oxalic acid (C 2H2O4), respectively, which are more commonly associated with dry reforming and anthraquinone processes, respectively, as important and industrially useful products.
Here, the inventors found that by employing a non-thermal plasma (NTP), the activation energy gap associated with the highly stable o=c=o bond of CO 2 can be overcome to generate an active species that can be used to react with water (H 2 O) molecules. Here, H 2 O was used as a green reducing agent and an oxygen acceptor, yielding H 2O2 as a product.
Two key steps of this process include mainly plasma pre-activation and interaction between H 2 O and plasma activated CO 2 gas. Various species (including electrons, ions, radicals, molecular fragments) having different energy levels are present in the plasma ionized gas.
Unlike thermal plasmas (equilibrium plasmas) that have high bulk gas temperatures (typically above 5 x 10 3 K), NTP operates at more ambient temperature conditions, but it provides sufficient energy to activate stable molecules and drive reactions across the energy gap, with excellent product selectivity and high energy efficiency.
Thus, this process is in sharp contrast to conventional industrial processes, where the reduction of CO 2 typically uses valuable hydrogen or methane gas, which inevitably consumes more energy.
Fig. 1 shows a schematic diagram of a simplified plasma-bubble reactor 5 configured for activation of carbon dioxide (CO 2) using a High Voltage (HV) electrode immersed in a liquid medium comprising water (H 2 O), wherein plasma-activated CO 2 is reacted with H 2 O to produce H 2O2, oxalic acid (C 2H2O4) and synthesis gas (CO, H 2、O2).
Without being bound by any one particular theory, the inventors believe that the ground state carbon dioxide molecules (CO 2) may be activated under a strong alternating electric field associated with the plasma to form excited state molecules (CO 2, CO) and release atomic oxygen atoms (O). These active species may further react with water molecules in the liquid medium to form H 2O2、CO、O2、H2 and one or more hydrocarbons including, but not limited to, formic acid (CH 2O2), acetic acid (CH 3 COOH), and oxalic acid (C 2H2O4).
By controlling reactor design and plasma conditions and coupling to the catalyst, the chemical can be exported as three valuable chemicals/fuels; h 2O2 in liquid phase and the hydrocarbon, and synthesis gas in gas phase (H 2+CO+O2).
The following is a detailed description of four (4) different configurations of the plasma-bubble reactor 5 in fig. 1, a reactor system 400 configured for continuous production of H 2O2, the hydrocarbons and synthesis gas, and a method of producing the same.
Plasma-bubble reactor
Fig. 2 shows a schematic diagram of four (4) different configurations of the plasma-bubble reactor 5 of fig. 1, including (a) a single reactor 10, (b) a single reactor 110 with adjustable High Voltage (HV) electrode height (h), (c) a single reactor 210 equipped with HV electrodes modified with a catalyst, and (d) a double reactor 310 equipped with HV electrodes and Low Voltage (LV) electrodes.
The following description outlines the structural details of each of the four (4) different configurations.
In the simplest configuration, as shown in fig. 2 (a), the plasma-bubble reactor 10 comprises a vessel 15, the vessel 15 comprising a base 15a and a wall 15b upstanding from the base 15b to define a cavity 20 configured for containing a liquid medium 25, and an opening 15c in an upper portion of the vessel 15.
The plasma-bubble reactor 10 further comprises plasma generating means in the form of two electrodes 30, 40, the electrodes 30, 40 being located within the cavity 20 of the vessel 15 via openings 15c and being partially immersed in the liquid medium 25.
The two electrodes 30, 40 are electrically connected to an AC power source 50. However, one skilled in the relevant art will appreciate that in alternative embodiments, both electrodes 30, 40 may be electrically connected to a DC power source (not shown).
The first electrode 30 is a High Voltage (HV) electrode (or cathode) and the second electrode 40 is a counter electrode (or anode).
The HV electrode 30 is partially enclosed within a quartz tube 35, the quartz tube 35 defining a gas channel extending partially along the length of the HV electrode 30. The tube 35 comprises a gas inlet (not shown) in its upper part configured for receiving an input feed comprising carbon dioxide (CO 2) gas from a CO 2 gas source (not shown) and one or more gas outlets 35a, 35b in its lower part, wherein the lower part of the HV electrode 30 is fully submerged in the liquid medium 25.
Alternative arrangement
The components of the three other plasma-bubble reactor configurations 110, 210, 310 of fig. 2 (b), 2 (c), 2 (d) are labeled in a similar manner as the components in fig. 2 (a), with the prefix "1", "2", or "3" being employed prior to the reference numerals of each component to denote that the component is associated with the corresponding plasma-bubble reactor 110, 210, 310 of fig. 2 (b), 2 (c), 2 (d), respectively.
In fig. 2 (b), the plasma-bubble reactor 110 further comprises means (not shown) for adjusting the vertical position "h" of the HV electrode 130 with respect to the tube 135 in which it is partially enclosed. In one embodiment, the height of HV electrode 130 relative to tube 135 may be adjusted in the range of about 0mm to about 60 mm. With this arrangement, it is possible to increase or decrease the length of the plasma flow within the gas channel of the tube 135, thereby providing a means to increase or decrease the degree of ionization/excitation of the gas.
In fig. 2 (c), the tube 235 of the HV electrode 230 also contains a catalytically active material for catalyzing the reaction between the activated CO 2 gas and H 2 O.
In one embodiment, the catalytically active material is in the form of a plurality of particles, beads, pellets, or flakes supported within the tube 235. In this arrangement, the particles, beads, pellets or flakes act as supported catalysts and are typically produced from polymers, ceramics, glass or metal oxides.
In a particularly preferred embodiment, the catalytically active material comprises a plurality of Al 2O3 beads.
In fig. 2 (d), the two electrodes partially immersed in the liquid medium 25 in the vessel 315 consist of an HV electrode 330 powering the first reactor and a Low Voltage (LV) electrode 340 powering the second reactor. The inventors believe that the use of a second reactor driven by the low voltage electrode 340 will result in an increase in the rate of production of H 2O2 and synthesis gas and an increase in energy efficiency.
Method of
A process for producing hydrogen peroxide (H 2O2), one or more hydrocarbons and synthesis gas using the single reactor of fig. 2 (a) will now be described as a general guide.
According to a first step of the method, a potential difference is applied across the two electrodes 30, 40, causing the HV electrode 30 to generate a discharge within the tube 35. The discharge generates a plasma from the CO 2 gas that has been fed into the tube 35 from the input feed to produce an activated CO 2 gas. The activated CO 2 gas exits the tube 35 via gas outlets 35a, 35b and forms a plurality of bubbles in the liquid medium 25, which for the purposes of this embodiment, liquid medium 25 is an aqueous liquid medium comprising an electrolyte.
In one embodiment, the discharge is a pulsed discharge that is repeatedly applied at a frequency of about 50Hz to about 10 MHz. Under such conditions, the potential difference applied across the two electrodes 30, 40 is typically about 1kV to about 100kV.
According to a second step of the method, the activated CO 2 gas encapsulated within the bubbles produces a plurality of excited molecules selected from the group consisting of CO 2, CO, and oxygen atoms (O). These excited molecules then react with water (H 2 O) in the aqueous liquid medium 25 at the plasma-liquid interface formed between the bubbles and the surrounding liquid medium 25 to produce a liquid phase comprising at least hydrogen peroxide (H 2O2) and one or more hydrocarbons, including but not limited to formic acid (CH 2O2), acetic acid (CH 3 COOH), and oxalic acid (C 2H2O4), and a gas phase comprising synthesis gas.
In one embodiment, the reaction is carried out substantially at atmospheric pressure and room temperature, although one skilled in the relevant art will appreciate that varying one or both of these parameters may be used as a means to increase or decrease the rate of conversion of CO 2 gas to H 2O2, the one or more hydrocarbons, and synthesis gas.
Results
The inventors have found that by varying one or more of the plasma input voltage (amplitude and pulse width), frequency (discharge and resonance), gas flow rate of the input feed of CO 2 gas and/or liquid flow rate of H 2 O, the rate of conversion of CO 2 gas to H 2O2, the one or more hydrocarbons and synthesis gas can be varied.
For example, the inventors have found that the input voltage changes the ratio of plasma species, providing different reaction selectivities and power efficiencies. While the frequency changes the total power input and plasma density, the power efficiency is not changed.
Without wishing to be bound by any one particular theory, the inventors believe that the reaction at the plasma-liquid interface may contribute to two main pathways. One approach involves water sputtering and electron bombardment splitting followed by the combination of two OH radicals produced by electron bombardment, which helps form a relatively small portion of H 2O2. Most of the H 2O2 comes from the interaction between the H 2 O molecule and the atomic oxygen generated by the CO 2 gas. The second pathway helps to generate small amounts of H 2 in the liquid aqueous medium due to the combination of the two H radicals generated by electron bombardment.
Fig. 3 shows a graph of the gas ratio in the gas phase output streams from the plasma-bubble reactors 10, 110, 210 of fig. 2 (a), 2 (b) and 2 (c) when the plasma driving process employs CO 2 gas input feed.
CO 2 gas flow rate
For example, when the flow rate of the CO 2 gas of the input feed to vessel 15 of the plasma-bubble reactor 10 shown in fig. 2 (a) was reduced from 200sccm to 5sccm, the corresponding results in fig. 3 (a) show that a greater proportion of the input feed CO 2 gas underwent plasma activation (and subsequent reaction with H 2 O), as evidenced by a reduction in the total volume of CO 2 gas present in the output stream from 91% to 53%.
The results in fig. 3 (a) also reveal that the volume of CO gas in the output stream is increased three times and that the volumes of H 2 and O 2 are significantly increased.
Based on the observations, it is apparent that by reducing the flow rate of the input CO 2 gas, the volume of each syngas component that can be produced can be increased.
Gap size ('h')
In the case of the plasma-bubble reactor 110 shown in fig. 2 (B), with a fixed CO 2 gas flow rate (5 sccm), the corresponding results in fig. 3 (B) show that the proportion of the input feed CO 2 gas that undergoes plasma activation (and subsequent reaction with H 2 O) remains approximately unchanged regardless of the gap size ("H") as the HV electrode 130 is raised from 5mm to 20mm within the tube 135. However, when the gap size ("h") increases from 5mm to 20mm, the volume of CO produced increases by a factor of about 1.5. In contrast, for the same gap size ("H") variation, the volume of H 2 gas in the output stream showed a significant decrease from 17% to 4%, while the volume of O 2 showed only a slight decrease from 17% to 11%.
A corresponding study to determine how gap size ("H") affects hydrogen peroxide (H 2O2) production showed that when the CO 2 gas flow rate was maintained at the same 5sccm flow rate, the gap size ("H") increased from 0mm to 30mm, resulting in a decrease in the volume of H 2O2 (see table 1).
TABLE 1
Based on the observations, it is apparent that by varying the gap size ("H"), the volumes of H 2O2, oxalic acid (C 2H2O4), and the individual syngas components that can be produced can be selectively controlled.
Catalytic reaction
In the case of the plasma-bubble reactor 210 shown in fig. 2 (C), when the tube 235 of the HV electrode 230 was modified with a plurality of Al 2O3 beads (labeled "x") loaded within the tube 235 by a mesh plate and glass wool, the corresponding results in fig. 3 (C) show that the volume of CO 2 gas present in the output stream was significantly reduced by about 7% (compared to control experiments involving only plasma activation without beads), along with a 3% increase in CO volume, and a 7% increase in the volume of H 2, while the CO 2 gas flow rate and gap size ("H") were maintained at 5sccm and 20mm, respectively.
Examples
As shown in fig. 4A, a renewable energy driven plasma microbubble reactor was developed to generate subsurface microbubbles for the electroreduction of carbon dioxide to green fuel. The micro-scale pores distributed on the pillars not only act as channels for microplasma generation, but also create small microbubbles that transfer reactive plasma species.
The electrical characteristics of the plasma microbubble reactor (5.8kV,1500Hz,35.5W,10sccm CO 2) are shown in fig. 5.
CO 2 was used as feed gas, with flow rates varying from 1 to 1000 sccm.
Once CO 2 is fed through the plasma column and an electrical discharge is generated, the plasma-generated species will be transported through the gas bubbles and then transported into the aqueous medium and/or reacted with water molecules in the aqueous medium. These bubbles are expected to act as unique microreactors with large gas-liquid interfaces, thereby facilitating CO 2 conversion at the plasma-liquid interface.
The aqueous H 2O2 solution generated by the CO 2 plasma-water system was quantitatively analyzed using titanium (IV) sulfate and adding NaN 3.
Fig. 4B shows the time-dependent concentration of H 2O2 in solution relative to the plasma discharge. As shown, as the voltage amplitude driving the plasma bubble column increases, the H 2O2 concentration increases linearly, and after 30min of 200V plasma treatment, the H 2O2 concentration is 190.8mg L -1.
Further optimization of the CO 2 plasma-water system involved varying the flow rate of CO 2 and the solution pH (fig. 4C and 4D).
For example, as shown in fig. 4D, the H 2O2 production rate (mg H -1) initially increases with decreasing CO 2 flow rate (sccm) and then decreases as the gas flow rate is further decreased. It should be noted that the discharge power of the CO 2 plasma discharge remains almost unchanged regardless of the gas flow rate.
As shown in fig. 4D, the production rate of oxalic acid (mg H -1) was substantially twice that observed for H 2O2 (mg H -1) (see fig. 4C).
The highest rate of production of H 2O2 was achieved at a flow rate of 10sccm, with a relatively high energy efficiency of 3.6g kWh -1.
Liquid hydrocarbon fuels produced in CO 2 plasma-water systems were quantified using low temperature NMR spectroscopy and UV-Vis spectroscopy in combination with colorimetric determination.
The NMR spectrum of the treatment solution after CO 2 plasma discharge clearly demonstrated the presence of formic acid (CH 2O2) and acetic acid (CH 3 COOH), as shown in fig. 6A.
Other C 2 -hydrocarbon species (oxalic acid) were quantified using an enzymatic chemical assay, and figure 4D shows a similar trend in the rate of production of H 2O2 (mg H -1) and energy efficiency as a function of CO 2 flow rate (sccm). It should be noted that the yield of formic acid and acetic acid produced in the CO 2 plasma-water system is quite low, only a few ppm, compared to oxalic acid content on the order of hundreds of ppm.
Without being bound to any one particular theory, the inventors believe that one possible reaction pathway to produce such liquid hydrocarbon fuels occurs via a combination of vibrationally excited CO 2 species generated in the Dielectric Barrier Discharge (DBD) section, followed by reaction with H free radicals dissociated from H 2 O at the plasma-liquid interface.
As described above, the synthesis gas produced in the CO 2 plasma-water system in gaseous flow form mainly comprises carbon monoxide (CO), carbon dioxide (CO 2) and hydrogen (H 2), which can be widely used as an intermediate resource for the production of, for example, hydrogen (H 2), ammonia (NH 3), methanol (CH 3 OH) and other synthetic hydrocarbon fuels.
Figure 9 shows how the ratio of products in the output gas phase can be adjusted by the gas flow rate. Clearly, the CO 2 gas conversion showed a decreasing trend with increasing total gas flow rate (sccm), and the highest CO 2 conversion was obtained at a gas flow rate of 5 sccm. This may be due to the long residence time of the gas molecules in the discharge region contributing to the strong collisions between the energetic electrons and the CO 2 molecules, facilitating CO 2 conversion. This is also consistent with the results of CO 2 dissociation and CO 2 hydrogenation in other DBD discharges.
Materials and methods
Plasma parameters and characterization
The applied voltage and current were recorded with a digital oscilloscope (RIGOL DS 6104) using a high voltage probe (Tektronics P6015A) and a current probe (Pearson 4100), respectively. The discharge power was calculated based on the previously reported study.
H 2O2 quantification
The H 2O2 concentration was measured using the titanium sulfate method. When titanium (IV) ion Ti 4+ reacts with hydrogen peroxide, a yellow complex is formed with a UV-Vis absorbance of 410nm (Ti 4++H2O2+2H2O→H2TiO4+4H+). Colorimetric analysis was performed using a Shimadzu (Japan) UV-2600i UV-Vis spectrophotometer.
Gas Chromatography (GC) quantification
C18 and C were used by Shimadzu (Australia) Nexis GC-2030 equipped with FID, TCD and ECD detectorsThe column quantitates the gaseous product compounds. Hydrogen (H 2) and oxygen (O 2) were quantified by TCD detector. Carbon monoxide (CO) and carbon dioxide (CO 2) were quantified by an FID detector with methanation. Standard gas (/ >)501743 Purchased from Sigma-Aldrich (australia) with gas composition CO 2(7％)、CO(15％)、O2 (4%) and CH 4 (4.5%).
Oxalic acid quantification
Oxalic acid generated by CO 2 plasma discharge was quantified using the Sigma-Aldrich (australia) oxalate assay kit (MAK 315). The use of the assay kit follows the product information.
The calculation is based on the following equation:
Where D represents dilution ratio and OD represents optical density value collected at 595nm wavelength of UV-Vis spectrum.
NMR quantification
Formic acid and acetic acid were quantified by Nuclear Magnetic Resonance (NMR) spectroscopy using a Bruker (germany) AVIII MHz NMR spectrometer equipped with a low temperature trinuclear probe.
All NMR samples were prepared by mixing with D 2 O and dimethyl sulfoxide (DMSO, internal standard) solutions to a final 10% D 2 O and 10ppm DMSO concentration.
600MHz 1D-1H-NMR spectra were recorded using zgesgppe pulse sequences to suppress the water signal. Acquisition was maintained at 298K using a spectral width of 14ppm, a time domain data size of 67K, 8 virtual scans, and 32 scans.
Chemical product
Sulfuric acid (H 2SO4, ACS reagent, 95.0% -98.0%), titanium (IV) chloride (TiCl 4,99.9% Trace metal base), hydrogen peroxide solution (30% w/w in water with stabilizer), isotopic carbon dioxide (C 18O2, 95% atomic 18 O), deuterium oxide (D 2 O, 99.9% atomic D), dimethyl sulfoxide (DMSO, ACS reagent, > 99.9%), sodium azide (NaN 3, > 99.0%), oxalate assay kit (MAK 315) were purchased from Sigma-Aldrich (australia) without further purification. Carbon dioxide (CO 2, high purity grade, 99.99%) Gas cylinders were purchased from BOC Gas (australia).
Reactor system
The inventors have found that by operably coupling two or more plasma-bubble reactors, a reactor system capable of continuously producing hydrogen peroxide (H 2O2), one or more hydrocarbons including, but not limited to, formic acid (CH 2O2), acetic acid (CH 3 COOH) and oxalic acid (C 2H2O4), and syngas can be achieved when a continuous feed of carbon dioxide (CO 2) and water (H 2 O) is supplied to the system.
For example, fig. 10 shows a schematic diagram of a reactor system 400 comprising three plasma-bubble reactors 410, 510, 610 operably coupled via a series of fluid conduits such that one or more of CO 2 gas, H 2O2, the one or more hydrocarbons, syngas, and/or H 2 O are in fluid communication therebetween.
As shown in fig. 10, the three plasma-bubble reactors 410, 510, 610 are slightly different from those shown in fig. 2. For example, referring to the first plasma-bubble reactor 410, the plasma generating device includes a single HV electrode 430 partially submerged within the liquid in the container 415, and a ground electrode 440 electrically connected to the outer wall of the container 415.
To facilitate the operable coupling between the plasma-bubble reactors 410, 510, 610, each of the respective vessels 415, 515, 615 includes a plurality of ports that may be connected to respective fluid conduits to enable fluid communication of CO 2 gas, H 2O2, syngas, and/or H 2 O from one vessel to the next.
In addition to the three plasma-bubble reactors 410, 510, 610, the reactor system 400 also includes a pump 800 for fluidly communicating water (H 2 O) from a water source (not shown) to the vessel 615 of the nearest (third) plasma-bubble reactor 610, a compressor 700, and a flow meter 710 disposed between the input feed (not shown) of CO 2 gas and the vessel 415 of the nearest (first) plasma-bubble reactor 410 to enhance the flow of CO 2 gas from the input feed to the vessel 415 and monitor the flow rate, respectively, and finally, a liquid receiver 900 for receiving H 2O2 produced by all three plasma-bubble reactors 410, 510, 610.
In use, H 2 O from a water source is in fluid communication along conduit 760 with the aid of pressure applied by pump 800 to port 615f of vessel 615 of third plasma-bubble reactor 610. When the container 615 is full, the H 2 O level rises until it reaches the level of the port 615 e. At this point, the pressure applied by pump 800 drives H 2 O along conduit 770 to port 515f of vessel 515 of central (second) plasma-bubble reactor 510. Similarly, once the H 2 O level reaches the level of port 515e in the vessel 515, H 2 O is fluidly connected to port 415f of vessel 415 of the first plasma-bubble reactor 410 along conduit 780.
Once each of the three vessels 415, 515, 615 contains a sufficient volume of H 2 O, then the CO 2 gas stream is directly in fluid communication along conduit 720 from the input feed to the tube 435 of the HV electrode 430 partially submerged in H 2 O in vessel 415 of the first plasma-bubble reactor 410.
A potential difference is then applied across the two electrodes 430, 440 of the first plasma-bubble reactor 410 to generate a plasma from the CO 2 gas within the tube 435. The activated CO 2 gas thus produced then exits the tube 435 via outlets 435a, 435b into the liquid medium in the container 415 in the form of a plurality of bubbles encapsulating the activated CO 2 gas.
The excited molecules (CO 2, CO, O) associated with the activated CO 2 gas encapsulated within the bubbles then react with water (H 2 O) in the vessel 415 at the plasma-liquid interface formed between the bubbles and the surrounding H 2 O to produce a liquid phase comprising at least hydrogen peroxide (H 2O2) and one or more of the hydrocarbons, and a gas phase comprising synthesis gas.
The resulting H 2O2 is driven by the pressure applied by pump 800 to the outlet port 415e of the container 415, which is then in fluid communication along conduit 790 to the liquid receiver 900. At the same time, the synthesis gas and any unactivated CO 2 gas remaining from the reaction are driven by the flow of CO 2 gas from the input feed to the outlet port 415d of vessel 415 with the aid of compressor 700 and are in fluid communication along conduit 730 to port 535c of tube 535 of HV electrode 530 partially immersed in H 2 O in vessel 515 of second plasma-bubble reactor 510.
A potential difference is then applied across the two electrodes 530, 540 of the second plasma-bubble reactor 510, thereby generating a plasma from the unactivated CO 2 gas within the tube 535. The activated CO 2 gas thus generated then exits the outlets 535a, 535b of the tube 535, encapsulated within a plurality of bubbles to react with H 2 O in the vessel 515 at the plasma-liquid interface formed between the bubbles and H 2 O to produce more H 2O2 and more syngas.
H 2O2 then merges with any H 2 O in vessel 515, is driven to outlet port 515e by pressure applied by pump 800, and is in fluid communication along conduit 780 to vessel 415 of first plasma-bubble reactor 410, where it then merges with any H 2O2 (merges with any H 2 O in vessel 415) produced by first plasma-bubble reactor 410, and is then in fluid communication along conduit 790 to liquid receiver 900. The synthesis gas and any unactivated CO 2 gas remaining from the reaction are driven by the CO 2 gas stream from the input feed to the outlet port 515d and are in fluid communication along conduit 740 to port 635c of tube 635 of HV electrode 630 partially submerged in H 2 O in vessel 615 of the third plasma-bubble reactor 610.
There, when a potential difference is applied across the two electrodes 630, 640, the unactivated CO 2 gas is activated by the plasma generated in the tube 635. The activated CO 2 gas thus produced, together with any synthesis gas from the previous reaction, then exits the outlets 635a, 635b of the tubes 635 in the form of bubbles. The excited molecules (CO 2, CO, O) associated with the activated CO 2 gas encapsulated within the bubbles then react with the water (H 2 O) in the vessel 615 at the plasma-liquid interface formed between the bubbles and the surrounding H 2 O to produce more H 2O2 and more syngas.
The synthesis gas produced in vessel 615 is driven by the positive pressure applied by compressor 700 to outlet port 615d along with any synthesis gas also present in vessel 615 produced by first and second plasma-bubble reactors 410, 510, wherein it is then in fluid communication along conduit 750 to a gas collection vessel (not shown).
However, H 2O2 combines with any H 2 O in vessel 615, is driven by the pressure applied by pump 800 to outlet port 615e to be in fluid communication along conduit 770 to port 515f of vessel 515 of second plasma-bubble reactor 510, which in turn, before final fluid communication, will be in fluid communication along conduit 780 with any H 2O2 generated by second plasma-bubble reactor 510 to port 415f of vessel 415 of first plasma-bubble reactor 410, along conduit 790 to liquid receiver 900, along with any H 2O2 generated by first plasma-bubble generator 410.
With the above arrangement, the present inventors have determined that the reactor system 400 is capable of continuously producing hydrogen peroxide (H 2O2) and syngas when an input feed of carbon dioxide (CO 2) and water (H 2 O) are continuously supplied to the system 400.
The advantages are that:
The present invention provides a number of advantages including, but not limited to:
Scalable "green" technology is implemented to produce industrially important products (H 2O2 and synthesis gas).
A device utilizing carbon dioxide (CO 2) gas is implemented, thereby helping to reduce the amount of (CO 2) gas present in the environment.
Embodiments are described below:
Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the appearances of the phrase "in one embodiment" or "in an embodiment" appearing in various places throughout the specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner as would be apparent to one of ordinary skill in the art in view of this disclosure in one or more embodiments.
Similarly, it should be appreciated that in the foregoing description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.
Furthermore, while some embodiments described herein include some other features, but not others included in other embodiments, combinations of features of different embodiments are intended to fall within the scope of the invention, and form different embodiments, as will be appreciated by those of skill in the art. For example, in the appended claims, any of the claimed embodiments may be used in any combination.
Other embodiments:
While the preferred embodiment of the invention described above involves the use of pure carbon dioxide (CO 2) as the input feed gas, one of ordinary skill in the relevant art will appreciate that the plasma-driven process may also use CO 2 gas in combination with the second gas.
For example, the input feed may comprise using a mixture of CO 2/CO、CO2/H2O(g)、CO2/CH4 and CO 2/H2 as the inlet gas.
Different instances of objects
As used herein, unless otherwise specified the use of the ordinal adjectives "first", "second", "third", etc., to describe a common object, merely indicate that different instances of like objects are being referred to, and are not intended to imply that the objects so described must be in a given sequence, either temporally, spatially, in ranking, or in any other manner.
Specific details of the invention
In the description provided herein, numerous specific details are set forth. It will be understood, however, that embodiments of the invention may be practiced without these specific details. In other instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
Terminology
In describing the preferred embodiments of the present invention illustrated in the drawings, specific terminology will be resorted to for the sake of clarity. However, the invention is not intended to be limited to the specific terms so selected, and it is to be understood that each specific term includes all technical equivalents that operate in a similar manner to accomplish a similar technical purpose. Terms (e.g., "forward," "rearward," "radial," "peripheral," "upward," "downward," etc.) are used as convenient terms for providing points of reference, and are not to be construed as limiting terms.
Inclusion and inclusion
In the claims and the preceding description that follow, unless the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
As used herein, any one of the terms "comprising" or "including" is also an open term that also means including at least the elements/features following the term, but not excluding other elements/features. Thus, inclusion is synonymous with and means inclusion.
Scope of the invention
Thus, while there have been described what are believed to be the preferred embodiments of the present invention, those skilled in the art will recognize that other and further modifications may be made thereto without departing from the spirit of the invention, and it is intended to claim all such changes and modifications as fall within the scope of the invention. For example, any formulas given above represent only processes that may be used. Functions may be added or deleted from the block diagrams and operations may be interchanged among the functional blocks. Steps may be added or deleted to the described methods within the scope of the invention.
Although the invention has been described with reference to specific examples, those skilled in the art will appreciate that the invention may be embodied in many other forms.
Industrial applicability
As is evident from the above, the arrangement described is applicable to the chemical industry.
Claims (33)
1. A plasma-bubble reactor comprising:
-a container configured for containing a liquid; and
-A plasma generating device associated with the vessel configured to receive an input feed comprising carbon dioxide (CO 2) gas and generate a plasma from the CO 2 gas to produce an activated CO 2 gas encapsulated within a plurality of bubbles formed in the liquid, wherein the activated CO 2 gas is reacted with water (H 2 O) at a plasma-liquid interface formed between the bubbles and surrounding liquid to produce hydrogen peroxide (H 2O2), one or more hydrocarbons and synthesis gas.
2. The reactor of claim 1, wherein the plasma generating device comprises two electrodes, wherein at least one of the two electrodes is a High Voltage (HV) electrode at least partially submerged within the liquid and configured to generate a discharge across the liquid when a potential difference is applied across the electrodes, thereby activating the CO 2 gas encapsulated within the bubbles.
3. The reactor of claim 2, wherein each of the two electrodes is at least partially submerged within the liquid.
4. A reactor according to claim 3, wherein each of the two electrodes is an HV electrode at least partially immersed in the liquid.
5. The reactor of claim 2, wherein the other of the two electrodes is a grounded electrode electrically connected to an outer wall of the vessel.
6. The reactor of any one of claims 2 to 5, wherein the HV electrode is partially enclosed within a tube defining a gas channel extending partially along the length of the HV electrode, wherein the tube is in fluid communication with the input feed and is provided with one or more outlets at a lower portion thereof to allow the activated CO 2 gas enclosed within the bubbles to be expelled therefrom into the liquid in the vessel.
7. The reactor of any one of claims 2 to 6, wherein the two electrodes are electrically connected to a DC or AC power source.
8. The reactor of claim 4, further comprising means for adjusting the vertical position of the HV electrode relative to the tube to produce a longer plasma flow within the gas channel.
9. The reactor of claim 8, wherein the vertical position of the HV electrode relative to the tube is adjustable in a range of about 0mm to about 60 mm.
10. The reactor of claim 6, wherein the tube of the HV electrode comprises a catalytically active material for catalyzing a reaction between the activated CO 2 gas and H 2 O.
11. The reactor of claim 10, wherein the catalytically active material comprises a plurality of alumina beads.
12. The reactor of any one of claims 1 to 11, wherein the one or more hydrocarbons are selected from the group consisting of formic acid, acetic acid, and oxalic acid.
13. A reactor system comprising:
-two or more plasma-bubble reactors, wherein each plasma-bubble reactor comprises:
-containers configured for containing liquids, wherein each container contains a plurality of ports;
-a plasma generating device associated with the vessel configured to receive an input feed comprising carbon dioxide (CO 2) gas and generate a plasma from the CO 2 gas to produce an activated CO 2 gas encapsulated within a plurality of bubbles formed in the liquid, wherein the activated CO 2 gas is reacted with water (H 2 O) at a plasma-liquid interface formed between the bubbles and surrounding liquid to produce hydrogen peroxide (H 2O2), one or more hydrocarbons and synthesis gas; and
-A plurality of fluid conduits, wherein each fluid conduit is configured for operably coupling adjacent plasma-bubble reactors via a respective port such that one or more of CO 2 gas, H 2O2, one or more hydrocarbons, synthesis gas, and/or H 2 O are in fluid communication therebetween.
14. The reactor system of claim 13, wherein the plasma generating device comprises two electrodes, wherein at least one of the two electrodes is a High Voltage (HV) electrode at least partially submerged within the liquid and configured to generate a discharge across the liquid when a potential difference is applied across the electrodes to activate the CO 2 gas encapsulated within the bubble.
15. The reactor system of claim 14, wherein the other of the two electrodes is a grounded electrode electrically connected to an outer wall of the vessel.
16. The reactor system of any one of claims 13 to 15, further comprising a pump for fluidly communicating water from a water source to a vessel of one of the two or more plasma-bubble reactors.
17. The reactor system of any one of claims 13 to 16, further comprising a compressor for enhancing the flow of CO 2 gas from the input feed to the vessel of one of the two or more plasma-bubble reactors.
18. The reactor system of claim 17, further comprising a flow meter to monitor a flow rate of the CO 2 gas, the flow meter being disposed in a line between the compressor and a vessel of the one plasma-bubble reactor.
19. The reactor system of any one of claims 13 to 18, further comprising a liquid receiver for receiving H 2O2 from a vessel of one of the two or more plasma-bubble reactors.
20. The reactor system of any one of claims 13 to 19, wherein the one or more hydrocarbons are selected from the group consisting of formic acid, acetic acid, and oxalic acid.
21. A process for producing hydrogen peroxide (H 2O2), one or more hydrocarbons and synthesis gas, the process comprising the steps of:
-generating a plasma from an input feed comprising carbon dioxide (CO 2) gas to produce an activated CO 2 gas encapsulated within a plurality of bubbles formed in the liquid; and
-Reacting the activated CO 2 gas with water (H 2 O) at a plasma-liquid interface formed between the bubbles and surrounding liquid to produce hydrogen peroxide (H 2O2), one or more hydrocarbons and synthesis gas.
22. The method of claim 21, wherein the plasma is generated by applying a potential difference across two electrodes, wherein at least one of the two electrodes is a High Voltage (HV) electrode at least partially submerged within the liquid and configured to generate a discharge throughout the liquid to activate the CO 2 gas encapsulated within the bubble.
23. The method of claim 21 or 22, wherein the discharge is a pulsed discharge.
24. The method of claim 22 or 23, wherein the potential difference is about 1kV to about 100kV.
25. The method of any one of claims 21 to 24, wherein the liquid is an aqueous medium.
26. The method of claim 25, wherein the aqueous medium comprises an electrolyte.
27. The method of any one of claims 21 to 26, wherein the reaction is carried out in a vessel at substantially atmospheric pressure and room temperature.
28. The method of any one of claims 21 to 27, wherein the input feed comprises a mixture of the CO 2 gas and a second gas.
29. The method of claim 28, wherein the second gas is selected from the group consisting of carbon monoxide (CO), water vapor/steam (H 2 O), methane (CH 4), hydrogen (H 2), nitrogen (N 2), and any mixtures thereof.
30. The method of any one of claims 22 to 29, wherein the HV electrode is partially enclosed within a tube defining a gas channel extending partially along the length of the HV electrode, the method further comprising the steps of:
-adjusting the vertical position of the HV electrode relative to the vertical position of the tube to produce a longer plasma flow within the gas channel.
31. The method of claim 30, wherein the vertical position of the HV electrode is adjustable in a range of about 0mm to about 60mm relative to the vertical position of the tube.
32. The method according to any one of claims 21 to 30, further comprising the step of:
-catalyzing a reaction between the activated CO 2 gas and H 2 O.
33. The method of any one of claims 21 to 32, wherein the one or more hydrocarbons are selected from the group consisting of formic acid, acetic acid, and oxalic acid.
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| AU2021902528 | 2021-08-13 | ||
| AU2021902528A AU2021902528A0 (en) | 2021-08-13 | Apparatus, system and method for producing hydrogen peroxide and syngas | |
| PCT/AU2022/050868 WO2023015343A1 (en) | 2021-08-13 | 2022-08-09 | Apparatus, system and method for producing hydrogen peroxide, hydrocarbon(s) and syngas |
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| KR (1) | KR20240042518A (en) |
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| US20050189278A1 (en) * | 2004-02-03 | 2005-09-01 | Takanori Iijima | Apparatus for decomposing organic matter with radical treatment method using electric discharge |
| JP5638678B1 (en) * | 2013-09-10 | 2014-12-10 | Ｐｍディメンションズ株式会社 | Liquid dielectric barrier discharge plasma apparatus and liquid purification system |
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| EP3162435B1 (en) * | 2014-06-27 | 2020-03-11 | Kyushu Institute of Technology | Method for manufacturing reaction product in which phase interface reaction is employed and phase interface reactor |
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| US20170128906A1 (en) * | 2015-11-09 | 2017-05-11 | EP Technologies LLC | Method and system for creating large volumes of highly concentrated plasma activated liquid using cold plasma |
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